Polythiophenes and devices thereof

Abstract

An electronic device containing a polythiophene prepared by a metal halide-mediated coupling polymerization in an appropriate solvent, and which polythiophene is comprised of at least one monomer unit selected from the group consisting of 2,5-thienylene (or 2,5-thiophenediyl) (I), 2,5-thienylene (or 2,5-thiophenediyl) (II), and a divalent linkage D wherein, for example, A is alkyl, alkoxy or derivatives thereof; B is a hydrogen atom, a small substituent like alkyl or alkoxy.

1. A device containing a polythiophene prepared by a metal halide polymerization in an aromatic solvent, and which polythiophene has a number average molecular weight (M n ) of from about 2,000 to about 100,000, and a weight average molecular weight (M w ) of from about 4,000 to about 500,000, both as measured by gel permeation chromatography using polystyrene standards, and which polythiophene is comprised of at least one monomer unit comprising at least one of 2,5-thienylene segment (I), and at least one of 2,5-thienylene segment (II), and a divalent linkage D 
                 
 
       wherein A is alkyl or alkoxy; B is a halide; and D is a divalent linkage for said (I) and (II). 
     
     
       2. A device in accordance with  claim 1  wherein said metal halide is ferric chloride, MoCI 3  or RuCl 3 . 
     
     
       3. A device in accordance with  claim 1  wherein said aromatic solvent is a halogenated solvent selected from the group consisting of bromobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, and chloronaphthalene. 
     
     
       4. A device in accordance with  claim 1  wherein the solvent is tetrahydronaphthalene. 
     
     
       5. A device in accordance with  claim 1  wherein A alkyl contains from about 5 to about 25 carbon atoms; B alkyl contains from 1 to about 3 carbon atoms; and D is arylene. 
     
     
       6. A device in accordance with  claim 1  wherein said A is selected from the group consisting of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pentyloxy, hexyloxyl, heptyloxy, octyloxy, methoxybutyl, methoxybutoxy, methoxyhexyl, methoxyheptyl, and perfluoroalkyl; B is selected from the group consisting of methyl, ethyl, methoxy, ethoxy, and propyl; and D is selected from the group consisting of phenylene, biphenylene, phenanthrenylene, dihydrophenanthrenylene, fluorenylene, oligoarylene, methylene, polymethylene, dialkylmethylene, dioxyalkylene, dioxyarylene, and oligoethylene oxide. 
     
     
       7. An electronic device containing a polythiophene prepared by a metal halide-mediated coupling polymerization in a halogenated aromatic solvent or a hydronaphthalene, which polythiophene has a number average molecular weight (M n ) of from about 2,000 to about 100,000 and a weight average molecular weight (M w ) of from about 4,000 to about 500,000, both as measured by gel permeation chromatography using polystyrene standard, and which polythiophene is derived from a monomer segment of Formula (III) 
                 
 
       wherein R is alkyl or alkoxy; R′ is alkoxy, halogen, or alkyl; a and b represent the number of R and R′ substituents; Z is a divalent conjugated linkage; x and y represent the number of repeating units of their respective segment and x is greater than zero; and n is the degree of polymerization. 
     
     
       8. A device in accordance with  claim 7  wherein said metal halide is ferric chloride, and said a and b are 1 or 2. 
     
     
       9. A device in accordance with  claim 7  wherein said halogenated aromatic solvent is selected from the group consisting of bromobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, and chloronaphthalene. 
     
     
       10. A device in accordance with  claim 7  wherein alkyl contains from about 1 to about 25 carbon atoms; x is from 1 to about 3, and y is from zero to about 3. 
     
     
       11. A device in accordance with  claim 7  wherein the divalent linkage, Z, contains one or more segments selected from the group consisting of 2,5-thienylene, arylene, furandiyl, pyrrolediyl, pyridinediyl, benzofurandiyl, dibenzofurandiyl, benzothiophenediyl, dibenzothiophenediyl, dialkylaminoarylene, and carbazolediyl. 
     
     
       12. A device in accordance with  claim 7  wherein the divalent linkage, Z, contains at least one substituted and/or non-substituted 2,5-thienylene segment. 
     
     
       13. A device in accordance with  claim 7  wherein R is selected from the group consisting of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pentyloxy, hexyloxy, heptyloxy, octyloxy methoxybutyl, methoxybutoxy, methoxyhexyl, and methoxyheptyl; R′ is selected from the group consisting of methyl, ethyl, methoxy, ethoxy, bromo, and propyl. 
     
     
       14. A device in accordance wit  claim 7  wherein a=b=1, x is from 1 to about 3, and y is from zero to about 3. 
     
     
       15. A device in accordance with  claim 7  wherein chlorobenzene or dichlorobenzene is selected as the solvent. 
     
     
       16. A device in accordance with  claim 7  wherein tetrahydronaphthalene is selected as the solvent or the reaction medium for polymerization. 
     
     
       17. A device in accordance with  claim 7  wherein the polymerization is conducted by heating at from about 40° C. to about 100° C. for an optional period of from about 30 minutes to about 72 hours. 
     
     
       18. A device in accordance with  claim 7  wherein the number average molecular weight (M n ) of the polythiophene is from about 7,000 to about 30,000, and the weight average molecular weight (M w ) is from about 10,000 to about 100,000, both as measured by gel permeation chromatography using polystyrene standards. 
     
     
       19. An electronic device containing a polythiophene prepared by a metal halide-mediated coupling polymerization in a halogenated aromatic solvent or a hydronaphthalene, which polythiophene has a number average molecular weight (M n ) of from about 2,000 to about 100,000, and a weight average molecular weight (M w ) of from about 4,000 to about 500,000, both as measured by gel permeation chromatography using polystyrene standards, and wherein the polythiophene is alternatively of the Formulas (1) to (21), and wherein n represents the number of segments 
                 
                 
                 
 
     
     
       20. A device in accordance with  claim 7  wherein said device is a thin film transistor comprising a substrate, a gate electrode, an insulating dielectric layer, source and drain electrodes, and in contact with said dielectric layer and said source and drain electrodes, a semiconductor layer comprised of said polythiophene. 
     
     
       21. A thin film transistor in accordance with  claim 20  wherein said metal halide is ferric chloride, and said polymerization solvent is selected from the group consisting of bromobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, and tetrahydronaphthalene. 
     
     
       22. A thin film transistor in accordance with  claim 20  wherein said solvent is chlorobenzene or dichlorobenzene. 
     
     
       23. A thin film transistor in accordance with  claim 20  wherein said polythiophene possesses a number average molecular weight (M n ) of from about 7,000 to about 30,000, and a weight average molecular weight (M w ) of about 10,000 to about 100,000. 
     
     
       24. A thin film transistor in accordance with  claim 20  wherein said substrate is a polyester, a polycarbonate, or a polyimide; said gate source and drain electrodes are each independently comprised of gold, nickel, aluminum, platinum, indium titanium oxide, or a conductive polymer; and said gate is a dielectric layer comprised of silicon nitride or silicon oxide. 
     
     
       25. A thin film transistor in accordance with  claim 20  wherein said substrate is glass or a plastic sheet; said gate, source and drain electrodes are each comprised of gold; and said gate dielectric layer is comprised of the organic polymer poly(methacrylate), or poly(vinyl phenol). 
     
     
       26. A thin film transistor in accordance with  claim 20  wherein said polythiophene layer is formed by solution processes of spin coating, stamp printing, screen printing, or jet printing. 
     
     
       27. A thin film transistor in accordance with  claim 20  wherein said gate, source and drain electrodes, said gate dielectric, and semiconductor layers are formed by solution processes of spin coating, solution casting, stamp printing, screen printing, or jet printing. 
     
     
       28. A thin film transistor in accordance with  claim 20  wherein the substrate is a polyester, a polycarbonate, or a polyimide, and the gate, source and drain electrodes are fabricated from the organic conductive polymer polystyrene sulfonate-doped poly(3,4-ethylene dioxythiophene), or from a conductive ink/paste compound of a colloidal dispersion of silver in a polymer binder, and the gate dielectric layer is an organic polymer or an inorganic oxide polymer composite. 
     
     
       29. A device in accordance with  claim 1  wherein said halide is chloride or fluoride, or wherein said halide is bromide or iodide. 
     
     
       30. A device in accordance with  claim 1  wherein alkyl and alkoxy each contain from 1 to about 25 carbon atoms, and optionally wherein alkyl and alkoxy each contain from 2 to about 12 carbon atoms. 
     
     
       31. A device in accordance with  claim 1  wherein D is phenylene, and optionally wherein D is a substituted aryl, or biphenylene. 
     
     
       32. A device in accordance with  claim 1  wherein there is selected for said polymerization a monomer of 3-alkylthiophene, 2,5-bis(2-thienyl)-3,4-dialkylthiophene, 2,5-bis(2-thienyl)-3,4-dialkoxythiophene, 2,5-bis(3-alkyl-2-thienyl)thiophene, 2,5-bis(3-alkoxy-2-thienyl)thiophene, 5,5′-bis(3-alkyl-2-thienyl)-2,2′-dithiophene, 5,5′-bis(3-alkoxy-2-thienyl)-2,2′-dithiophene, 1,4-bis(2-thienyl)-2,5-dialkylbenzene, 1,4-bis(2-thienyl)-2,5-dialkoxybenzene, 3,4-ethylenedioxythiophene, 3,4-(2,2-dialkylpropylene-1,3-dioxy)thiophene, or 3-methyl-4-alkoxythiophene. 
     
     
       33. A device in accordance with  claim 21  wherein said solvent is selected in an amount of from about 250 to about 5,000 milliliters per mole of thiophene monomer. 
     
     
       34. A device in accordance with  claim 22  wherein said solvent is selected in an amount of from about 250 to about 5,000 milliliters per mole of thiophene monomer. 
     
     
       35. A thin film transistor comprised of the polythiophene of  claim 1 . 
     
     
       36. A thin film transistor transistor comprised of the polythiophene of  claim 7 , or comprised of the polythiophene of  claim 19 . 
     
     
       37. A thin film transistor comprised of a polythiophene, which polythiophene has a number average molecular weight (M n ) of from about 2,000 to about 100,000, and a weight average molecular weight (M w ) of from about 4,000 to about 500,000, both as measured by gel permeation chromatography using polystyrene standars, and which polythiophene is comprised of a monomer unit containing at least one of 2,5-thienylene segment (I), and at least one 2,5-thienylene segment (II), and a divalent D 
                 
 
       wherein A is alkyl or alkoxy; B is a halide; and D is a divalent linkage for said (I) and (II).